JP2008208033A - Hair dye and applicator for hair using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a hair dye having excellent water resistance, usability and cumulative hair dyeability and to provide an applicator for the hair using the same. <P>SOLUTION: The hair dye comprises 0.1-3.0 wt.% of an aqueous acid dye, 0.1-2.5 wt.% calculated as a solid content of a terpolymer represented by formula, a hair dye auxiliary, a lower alcohol and water and has a pH of 2-4. The applicator for the hair is provided by using the same. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a cumulative hair dye that does not require shampooing immediately after use and that gradually dyes the hair each time it is used, and more specifically, has excellent water resistance and cumulative dyeing. The present invention relates to a hair dye excellent in hair properties and usability and a hair applicator using the same.

Conventionally, permanent hair dyes (oxidative hair dyes) and semi-permanent hair dyes (acid dyes), which are generally used in general, are complicated and troublesome in use, and the surroundings, clothes, and skin of the subject. Has a major drawback such as being dyed.
For this reason, in general, the user has to be treated at a hairdressing salon, or he / she has to perform self-treatment when taking a bath so that it can be washed away immediately even if it gets dirty.

As a hair dye that can reduce these burdens and can be used for cumulative hair dyeing by simple repeated use even if the amount dyed at one time is small, for example, an acid dye as a colorant by the applicant of the present invention is used in an amount of 0.01 to 3. 1% by weight, 1.5 to 10% by weight of nonionic or anionic silicone resin, 3 to 20% by weight of hair dyeing assistant, 30 to 80% by weight of lower alcohol, and 5 to 50% by weight of water. A cumulative hair-dyeing temporary hair dye characterized in that the pH is 2 to 5 and the viscosity is 100 mPa · s or less (see, for example, Patent Document 1) is known.
In addition, one or two or more acid dyes are 0.01 to 1%, an acid as a pH adjusting agent is 0.1 to 10%, an aromatic alcohol as a penetrating agent is 1 to 20%, and a lower as a solvent. An acidic hair dye composition comprising 1 to 20% of alcohol and 0.01 to 5% of a polymer compound as a thickener (for example, see Patent Document 2), or an amino modification represented by a specific formula Alternatively, an acidic hair dye composition (see, for example, Patent Document 3) characterized by containing 0.01 to 10.0% by mass of one or more ammonium-modified polymer silicones is known.

However, the hair dye of Patent Document 1 is excellent as a hair that can be cumulatively dyed, but still has a problem in that it is slightly inferior in water resistance. Further, the acidic hair dye compositions of Patent Documents 2 and 3 are common in that an acidic dye is used, but there are still problems in that water resistance and hair dyeability are inferior. Since it is a viscosity, there is a problem in terms of usability, such as being unsuitable for use with a hair applicator having an occlusion body such as batting.
JP 2001-172141 A (Claims, Examples, etc.) JP 2002-104942 A (Claims, Examples, etc.) JP 2003-40746 A (Claims, Examples, etc.)

  The present invention has been made in view of the above-described problems of the prior art, and is intended to solve this problem. It is excellent in water resistance and usability, and has excellent cumulative hair dyeing properties and a hair applicator using the same. The purpose is to provide.

  As a result of intensive studies on the above-mentioned problems of the prior art, the present inventors have used an aqueous acidic dye, a resin composed of a specific terpolymer, a hair dyeing assistant, a lower alcohol, water, and their inclusion. The inventors have found that the above-mentioned target hair dye and a hair applicator using the same can be obtained by adjusting the amount to a specific range, and the present invention has been completed.

（２） 樹脂が式（Ｉ）で示されるビニルピロリドンが６０〜９０重量％、式（II）で示されるジメチルアミノプロピルメタクリルアミドが５〜３０重量％、式（III）で示されるアルキルジメチルアミノプロピルメタクリル酸が１〜３０重量％とで構成されることを特徴とする上記（１）記載の染毛料。
（３） 樹脂の重量平均分子量が４０００００〜８０００００である上記（１）又は（２）記載の染毛料。
（４） 水溶性酸性染料の含有比率ｙ（重量％）が、樹脂固形分量ｘ（重量％）とした場合、下記式（IV）を充足することを特徴とする上記（１）〜（３）の何れか一つに記載の染毛料。
０．１（ｘ＋１）＜ｙ≦０．２６４ｘ＋０．４ ………（IV）
（５） 水（Ａ）と低級アルコール（Ｂ）の含有比率（Ａ）／〔（Ａ）＋（Ｂ）〕が重量比で０．３〜０．７である上記（１）〜（４）の何れか一つに記載の染毛料。
（６） 染毛助剤が一価アルコール、多価アルコール、エーテルアルコール、低級アルキレンカーボネート、Ｎ−アルキルピロリドン類、ラクトン類から選ばれる少なくとも１種である上記（１）〜（５）の何れか一つに記載の染毛料。
（７） 染毛料の粘度が２〜５０ｍＰａ・ｓであることを特徴とする上記（１）〜（６）の何れか一つに記載の染毛料。
（８） 上記（１）〜（７）の何れか一つに記載の染毛料を貯蔵する貯蔵部を有することを特徴とする毛髪用塗布具。
（９） 塗布具本体部の先端部には、毛髪に染毛料を塗布する塗布体と、該塗布体の周囲に配置された櫛部とを有する塗布本体部を備えたことを特徴とする上記（８）に記載の毛髪用塗布具。 That is, the present invention resides in the following (1) to (9).
(1) 0.1 to 3.0% by weight of at least one aqueous acid dye, vinylpyrrolidone represented by the following formula (I), dimethylaminopropylmethacrylamide represented by the following formula (II), and the following formula While containing a resin composed of a terpolymer composed of alkyldimethylaminopropyl methacrylic acid represented by (III), the content of the resin is 0.1 to 2.5% by weight in solid content, A hair dye comprising 1.0 to 20% by weight of a hair dyeing assistant, 20 to 60% by weight of a lower alcohol, and 20 to 60% by weight of water, and having a pH of 2 to 4.

(2) The resin is 60 to 90% by weight of vinylpyrrolidone represented by the formula (I), 5 to 30% by weight of dimethylaminopropylmethacrylamide represented by the formula (II), and alkyldimethylamino represented by the formula (III). The hair dye according to (1) above, wherein propylmethacrylic acid is composed of 1 to 30% by weight.
(3) The hair dye according to (1) or (2), wherein the resin has a weight average molecular weight of 400,000 to 800,000.
(4) When the content ratio y (% by weight) of the water-soluble acid dye is the resin solid content x (% by weight), the following formula (IV) is satisfied: The hair dye as described in any one of these.
0.1 (x + 1) <y ≦ 0.264x + 0.4 (IV)
(5) The above-mentioned (1) to (4), wherein the content ratio (A) / [(A) + (B)] of water (A) and lower alcohol (B) is 0.3 to 0.7 by weight. The hair dye as described in any one of these.
(6) Any of (1) to (5) above, wherein the hair dyeing assistant is at least one selected from monohydric alcohols, polyhydric alcohols, ether alcohols, lower alkylene carbonates, N-alkylpyrrolidones, and lactones. The hair dye described in one.
(7) The hair dye according to any one of (1) to (6) above, wherein the hair dye has a viscosity of 2 to 50 mPa · s.
(8) A hair applicator characterized by having a storage unit for storing the hair dye according to any one of (1) to (7) above.
(9) The applicator main body having an application main body having an application body for applying a hair dye to hair and a comb portion arranged around the application body at a tip portion of the applicator main body ( The applicator for hair as described in 8).

ADVANTAGE OF THE INVENTION According to this invention, there is no skin irritation, it is excellent in water resistance and applicability | paintability, and the hair dye excellent in cumulative hair dyeability and drying property is provided.
Moreover, the applicator for hair of the present invention does not cause “sagging” or unintentional liquid discharge, is excellent in carrying and handling properties, and is excellent in water resistance and cumulative hair dyeing property.

Hereinafter, embodiments of the present invention will be described in detail.
The hair dye of the present invention comprises 0.1 to 3.0% by weight of at least one aqueous acidic dye, vinylpyrrolidone represented by the following formula (I), dimethylaminopropyl methacrylamide represented by the following (II), And a resin composed of a terpolymer composed of alkyldimethylaminopropyl methacrylic acid represented by the following formula (III), and the resin content is 0.1 to 2.5 wt. %, Hair dyeing assistant 1.0 to 20% by weight, lower alcohol 20 to 60% by weight, water 20 to 60% by weight, and pH is 2 to 4. is there.

  The aqueous acidic dye used in the present invention is not particularly limited as long as it is used in hair dyes and is contained in a water-soluble acidic dye. For example, a pharmaceutical that does not exhibit a harmful effect on the human body, It is selected from those specified by "Ministerial Ordinance on Tar Tars that can be Used for Pharmaceuticals" (Notification of Showa 41, Ministry of Health and Welfare) that is permitted to be used for coloring quasi drugs and cosmetics. It can be used as one kind or a mixture of two or more kinds.

  Specific examples of aqueous acid dyes include Red No. 3 (erythrosin), Red No. 102 (New Coxin), Red No. 207 (Risole Red BA), Orange No. 205 (Orange II), Yellow No. 4 (Tartrazine), Yellow No. 402 (Pola Yellow 5G), Yellow No. 403 (1) (Naphthol Yellow S), Green No. 3 (First Green FCF), Green No. 204 (Pyranin Conc), Blue No. 1 (Brilliant Blue FCF), Blue No. 202 (Patent) Blue NA), Purple No. 401 (Alizol Purple), Brown No. 201 (Resorcin Brown), Black No. 401 (Naphthol Blue Black) and the like (each alone or a mixture of two or more types, the same applies hereinafter). However, it is not limited to these.

The content of these aqueous acidic dyes needs to be 0.1 to 3.0% by weight (hereinafter simply referred to as “%”) with respect to the total amount of the hair dye, 1% is desirable.
If the content of the aqueous acidic dye is less than 0.1%, the hair dyeing effect is not sufficiently exhibited, and if it exceeds 3%, contamination of the skin and the like tends to occur, which is not preferable.

A resin composed of a terpolymer used in the present invention (hereinafter simply referred to as “terpolymer”) is suitable for achieving both high water resistance and cumulative hair dyeing properties and at the same time reducing the viscosity of hair dyes. A vinyl pyrrolidone (VP) represented by the above formula (I), a dimethylaminopropyl methacrylamide (DMAPMA) represented by the above formula (II), and an alkyldimethylaminopropyl represented by the above formula (III). It is a resin made of a terpolymer composed of methacrylic acid (QDMAPMA).
Preferably, from the viewpoint of water solubility and water resistance after drying, 40 to 95% of vinylpyrrolidone represented by the above formula (I) and 0.1 to 55% of dimethylaminopropyl methacrylamide represented by the above formula (II) And a resin comprising a terpolymer composed of 0.25 to 50% of alkyldimethylaminopropyl methacrylic acid represented by the above formula (III) is desirable, and more preferably represented by the above formula (I). It is composed of 60 to 90% vinylpyrrolidone, 5 to 30% dimethylaminopropyl methacrylamide represented by the above formula (II), and 1 to 30% alkyldimethylaminopropyl methacrylic acid represented by the above formula (III). It is desirable to use a resin comprising a terpolymer.

The terpolymer used in the present invention is a hydrophobically modified cationic polymer having a long-chain alkyl therein. A typical terpolymer has the following formula:

The alkyldimethylaminopropyl methacrylic acid represented by the above formula (III) to be used is preferably prepared by tosylating DMAPMA as follows.

As the terpolymer used in the present invention, preferably, the above formula (I) is vinylpyrrolidone, the above formula (II) is dimethylaminopropylmethacrylamide, and the above formula (III) is acrylic acid having 12 to 12 carbon atoms. 18, more preferably an alkyl quaternized derivative having 12 carbon atoms, the content of which is 60 to 90% in the formula (I), 5 to 30% in the above formula (II), and the formula (III) in the above formula (III). 1 to 30%, and its weight average molecular weight is 200,000 to 2,000,000, preferably 400,000 to 800,000, and the terpolymer is water-soluble, or It is water dispersible and, when cast on the support surface, forms a clear moisture-resistant, hydrophobic film; the film is surface active and hydrolytically stable and homogeneous Terpolymers Is desirable.
Examples of commercially available terpolymers that can be used include Stylize W-10 (polyquaternium 55 (made by ISP) having a resin solid content of 10%), Stylase W-20 [Polyquaternium 55 (made by ISP)). In which the resin solid content is 20%].

These terpolymers are required to be 0.1 to 2.5% in solid form, preferably 0.1 to 1.5%, more preferably based on the total amount of the hair dye. 0.3 to 1.0% is desirable.
If the content of the terpolymer is less than 0.1%, sufficient water resistance cannot be obtained. On the other hand, if it exceeds 2.5%, the cumulative hair dyeing property is lowered, and the viscosity of the liquid is also reduced. Is too expensive to handle.

The hair dyeing assistant used in the present invention is contained from the viewpoint of exerting further hair dyeing effects, such as monohydric alcohols, polyhydric alcohols, ether alcohols, lower alkylene carbonates, N-alkylpyrrolidones, lactones. At least one selected from the group.
Specifically, as the monohydric alcohol, a monohydric alcohol that is not included in the lower alcohol to be used can be used, and examples thereof include benzyl alcohol, phenethyl alcohol, furfuryl alcohol, and cyclohexanol. Examples of the polyhydric alcohol include ethylene glycol, Examples include propylene glycol, 1,3-butylene glycol, glycerin, diglycerin, dipropylene glycol, and the like, and ether alcohols include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol. And the lower alkylene carbonates include ethylene carbonate, propylene carbonate (propylene carbonate), butylene carbonate, and the like. Examples of rualkylpyrrolidones (lactams) include N-methylpyrrolidone (N-methyl-2-pyrrolidone), N-ethylpyrrolidone, and N-octylpyrrolidone. Examples of lactones include γ-butyrolactone. These can be used alone or in admixture of two or more.
Preferably, benzyl alcohol, N-methylpyrrolidone (N-methyl-2-pyrrolidone), propylene carbonate (propylene carbonate), and the like are desirable from the viewpoints of safety, drying property, smell, and the like.

The content of these hair dyeing assistants is preferably 1 to 20%, more preferably 5 to 15%, based on the total amount of the hair dye.
When the content of the hair dyeing assistant is less than 2%, the hair dyeing effect is not sufficiently exhibited, and when it exceeds 20%, the drying property after application is lowered, which is not preferable.

As the lower alcohol used in the present invention, for example, one or more lower alcohols that can be used for hair dyes such as ethanol, propanol, butanol, isopropanol, and isobutanol can be used. In view of the above, it is desirable to use ethanol.
The content of the lower alcohol is required to be 20 to 60%, preferably 20 to 45%, based on the total amount of the hair dye.
If the content of the lower alcohol is less than 20%, the drying property is lowered, and if it exceeds 60%, the hair dyeing effect is not sufficiently exhibited, which is not preferable.

The balance of the hair dye in the present invention is adjusted with water, for example, purified water, distilled water, ion-exchanged water, pure water, ultrapure water, clean water, normal water, distilled water, etc. can be used as its content Needs to be 20 to 60%, more preferably 35 to 60%, based on the total amount of the hair dye.
If the water content is less than 20%, the hair dyeing effect is lowered, and if it exceeds 60%, the drying property and low-temperature stability are lowered.

  In addition, the hair dye of the present invention can appropriately contain other optional components as long as the effects of the present invention and the stability of the system are not impaired. For example, various surfactants, preservatives, antioxidants Further, it can contain a reduction inhibitor, a chelating agent, an ultraviolet absorber, a viscosity modifier, an oil component, a silicone derivative, a pigment, a fragrance, an animal or plant extract, a known polymer component, and the like.

In the hair dye of the present invention, the content of the resin composed of the aqueous acidic dye and the ternary polymer is a factor that affects the hair dyeability and water resistance, and is contained within the above ranges of the respective contents. From the standpoint of further improving hair dyeability and water resistance, when the content ratio of the aqueous acidic dye is y (wt%) and the resin solid content x (wt%) comprising the above terpolymer, the following formula ( It is particularly desirable to satisfy IV).
0.1 (x + 1) <y ≦ 0.264x + 0.4 (IV)
For example, when the content of the aqueous acid dye is 0.5% by weight, the resin solid content x is desirably 0.379 (≈0.3787878...) Or more (˜2.5% by weight).

  Further, in the hair dye of the present invention, water and lower alcohol are factors that affect the stability and hair dyeing property of the resin composed of the terpolymer dissolved in the hair dye, and the ranges of the respective contents described above. The content ratio (A) / [(A) + (B)] of water (A) and lower alcohol (B) is weight from the viewpoint of further improving stability and hair dyeability. The ratio is preferably 0.3 to 0.7.

In the hair dye of the present invention, the pH is set to 2 to 4 in terms of using an aqueous acid dye, preventing hair damage, and preventing skin irritation.
If the pH of this hair dye exceeds 4, the hair dyeing property is insufficient, which is not preferred. On the other hand, if the pH is less than 2, skin irritation or hair damage may occur, which is not preferred.
In the present invention, the pH adjustment is carried out using a conventional pH adjuster, for example, organic or inorganic bases such as triethanolamine, potassium hydroxide, or sodium hydroxide, organic or inorganic bases such as citric acid, malic acid, hydrochloric acid, or glycolic acid. The acid can be optionally used.

The viscosity of the hair dye of the present invention is 2 to 50 mPa · s, preferably 3 to 30 mPa · s, from the viewpoint of easy application to the hair.
If the hair dye has a viscosity of less than 2 mPa · s, it tends to adhere to the scalp, and also tends to stain clothes, while if it exceeds 50 mPa · s, it is difficult to spread thinly and evenly on the hair. It is not preferable.

The hair dye in the present invention is prepared by blending each component such as the above-mentioned aqueous acidic dye, ternary copolymer, hair dyeing assistant, lower alcohol, water and the like within the above ranges of content, and stirring and mixing uniformly. Can be manufactured.
In the hair dye of the present invention configured as described above, it can be suitably used as a hair coloring agent for black hair, a hair coloring agent for white hair, etc., without being dyed to the skin, and having excellent cumulative hair dyeing properties, It has excellent water resistance against sweat, rain, and the like due to a hot and humid season such as summer, and a product with excellent usability can be obtained. In particular, even when applied to a wide range of hair, it does not irritate the skin, has excellent drying properties, can be used for a long time after drying, and functions as a temporary colorant that can sufficiently withstand rain and sweat. Moreover, after hair washing, the color remains in the hair, and it has excellent cumulative hair dyeing property and usability that is gradually dyed by repeated use.

Moreover, when using the hair dye of this invention comprised in this way, the applicator for hair is used, However, The shape, structure, etc. of the applicator for hair to be used are not specifically limited.
In the present invention, as a hair applicator that can be used, the applicability to the hair, the control of the amount of liquid contained in the application site, the occurrence of less fouling of clothes, skin, furniture, etc., and usability In view of the above, preferably, an application device for hair having a storage unit for storing the hair coloring material of the present invention is used, and more preferably, an application body for applying the hair coloring material to the hair at the tip of the application device main body portion; And a hair applicator provided with an application main body portion having a comb portion disposed around the application body.

FIG. 1 is a hair applicator A showing an example of an embodiment of a hair applicator using the hair dye of the present invention.
This hair applicator A is an applicator provided with a knock type valve device. As shown in FIG. 1, a base 11 is fixed to the tip of the applicator main body 10, and seven pieces are provided on the base 11. A coating body 12 made up of × 2 rows of brush bodies 12a, 12a... Is provided. Further, a front shaft 13 is fixed to the outer periphery of the pedestal 11, and a comb body 15 having 9 × 2 rows of comb teeth portions 15a, 15a... Is detachably attached to the front shaft 13. ing. An impregnated body 16 made of sponge or the like that contacts the coated body 12 is fitted in the center hole of the base 11, and a hair dye guide pipe 18 that communicates with the tip of the valve device to be described later with an impregnated body stopper 17 sandwiched behind the base 11. Is provided. Reference numeral 19 denotes a cap body. Further, the applicator main body portion 10 has a cylindrical inner shaft 20 serving as a hair dye storage portion, and a valve rod 21, a valve seat 22, a valve spring at the tip thereof. 23, a valve device 25 comprising a spring receiver 24 is attached, and a knock body 26 is provided at the rear end. Reference numeral 27 denotes a stirrer.
In the hair applicator A having such a configuration, the hair dye is filled via the hair dye guide tube 18 by filling the hair dye having the above-described structure of the present invention in the storage unit 20 and knocking the knock body 26. It flows out to the impregnation body 16 and is supplied to the application body 12 comprising the brush bodies 12a, 12a.

  Since this hair applicator A has a structure in which the hair dye is supplied from the impregnated body 16 to the applied body 12 composed of the brush bodies 12a, 12a..., This causes dripping and unintentional liquid discharge. In addition, since it has the comb body 15, the hair dye is not directly attached to the finger, etc., and it is excellent in carrying and handling properties, and is excellent in usability, water resistance, and cumulative hair dyeing properties. can do.

FIG.2 and FIG.3 is the hair applicator B which shows the other example of embodiment of the hair applicator using the hair dye of this invention.
As shown in FIGS. 2 and 3, the hair applicator B has a hair dye storage section in which the occlusion body 31 that occludes the hair dye of the present invention having the above-described configuration is stored inside the shaft body 30 that constitutes the applicator body. A core body 32 that is housed in 30a and has a comb-like shape for application having a plurality of capillary actions is fixed to the front end portion of the shaft body 30 in a linear row arrangement, and the rear end portion of the core body 32 is an occlusion body 31, the tip of the core body 32 protrudes forward of the shaft body 30, a comb portion 33 is provided on the side of the core body 32, and the cap body 40 is screwed to the tip of the shaft body 30. The center cap 43 is provided with a core tip receiving member 41 such as a felt that contacts the tip of the core body 32 and is provided with a recess 42 for accommodating the tip of the comb portion 33 on its side. 40 can move in the axial direction and turn in the circumferential direction To is obtained by the energized medium cap 43 by the spring member 44 toward the opening of the cap body 40.

  In the hair applicator B having such a configuration, the necessary hair dye is provided from the occlusion body 31 in which the hair dye having the above-described configuration of the present invention is occluded to the storage portion 30a to the tip of the core 32 serving as the application portion. While being supplied, it does not cause "dripping" or unintentional liquid discharge, and it is excellent in carrying and handling properties, and it should be a hair applicator excellent in usability, water resistance, and cumulative hair dyeing property. it can.

4-6 is the hair applicator C which shows the other example of embodiment of the hair applicator using the hair dye of this invention.
This hair applicator C is a modification of the hair applicator B shown in FIGS. 2 and 3, and as shown in FIGS. 4 to 6, the hair applicator C is disposed inside the shaft body 50 constituting the applicator main body. The occlusion body 51 that occludes the hair dye of the present invention that is configured is housed in the hair dye storage section 50a, and the core body 52 that is a comb-like form for application having a plurality of capillary action is arranged in a linear row in the form of a shaft. 50, the rear end portion of the core body 52 is connected to the occlusion body 51, and the front end portion of the core body 52 is projected forward of the shaft body 50, so that the side portion of the core body 52 is The comb portion 53 is detachably provided, and the cap body 54 is detachably attached to the distal end portion of the shaft body 50 by screwing, and a middle cap 55 that accommodates the distal end portion of the comb portion 53 on the side portion of the core body 52 is provided. An inner cap 5 is arranged in the cap body 54 so as to be movable in the axial direction and rotatable in the circumferential direction. The is obtained by an urging state to the opening direction of the cap body 54 by the spring member 56. In addition, 57 is an outer cylinder member arrange | positioned between the cap main body 54 and the intermediate | middle cap 55, 58 and 59 are an intermediate | middle cover member and a back cover member which stop the rear-end part of the axial body 50, respectively.

  In the hair applicator C having such a configuration, the necessary hair dye is provided from the occlusion body 51 in which the hair dye having the above-described configuration of the present invention is occluded to the storage portion 50a to the tip of the core body 52 serving as the application portion. While being supplied, it does not cause dripping or unintentional liquid discharge, and is excellent in carrying and handling properties, as well as in usability, water resistance and cumulative hair dyeing properties, and in a comb-like core Since 52 and the comb part 53 can be provided detachably, it can be set as the applicator for hair which becomes easy to assemble.

FIGS. 7-8 is the hair applicator C which shows the other example of embodiment of the hair applicator using the hair dye of this invention.
As shown in FIGS. 7 and 8, the hair applicator D is composed of a pedestal 60 serving as an operation part of the applicator, a receiving plate 61a attached to the upper surface 60a of the pedestal 60, and a spring member. A storage receiving member 61 having an elastic member 61b, a receiving plate member 62, a hair dye container 63, an occlusion body 64 storing the hair dye of the present invention housed in the hair dye container 63, and a peripheral edge The comb body 65 having comb portions 65a, 65a,... And a lid member 66, and the hair dye container 63 containing the occlusion body 64 storing the hair dye in the comb body 65 are housed.
In the hair applicator D having such a configuration, the occlusion body 64 serving as an application body that occludes the hair dye having the above-described configuration of the present invention is provided inside the peripheral comb portion 65a, so that the hair is combed by the comb portion 65a. It is an applicator for hair that can be easily and reliably dyed hair, is excellent in carrying and handling properties, is excellent in usability, water resistance and cumulative hair dyeing properties, and has a comb body 65 and occlusion body in a comb form. Since 64 can be provided detachably, it can be set as the applicator for hair which becomes easy to assemble.

  Next, the present invention will be described in more detail with reference to test examples (Examples and Comparative Examples), but the present invention is not limited to the following Examples.

[Examples 1 to 21 and Comparative Examples 1 to 12]
Each hair dye was prepared by uniformly stirring and mixing with a general-purpose propeller mixer with the composition shown in Tables 1 to 3 below.
About each hair dye of Examples 1-21 and Comparative Examples 1-12 obtained above, it measured about pH, a viscosity, etc. with the following method.
These results are shown in Tables 1 to 3 below.

(Measurement method of pH)
The pH (25 ° C.) was measured by a conventional method using a glass electrode pH meter.
(Viscosity evaluation method)
Each viscosity at 25 ° C. was measured with an ELD type viscometer or an EMD type viscometer (both manufactured by Toki Sangyo Co., Ltd.). The viscosity exceeding 12 mPa · s was measured with an EMD viscometer.

Subsequently, using each hair dye obtained above, water resistance, cumulative hair dyeability (5 times), coating performance, low temperature stability, drying property, and irritation were evaluated by the following methods. Moreover, comprehensive evaluation was performed based on the following evaluation criteria from these six evaluations.
These results are shown in Tables 1 to 3 below.

(Configuration of hair applicator, according to FIGS. 2-6)
Core: Fiber bundle core, polyester Comb: Molded product made of polypropylene

(Water resistance evaluation method)
Apply about 0.4g to 2g of hair, and after drying for 120 minutes at room temperature (hereinafter simply referred to as "apply to hair, after drying"), press the filter paper moistened with water to add color to the filter paper. The condition was evaluated according to the following evaluation criteria.
Evaluation criteria:
A: No adhesion to the filter paper. O: Thin adhesion to the filter paper. Δ: A little adhesion to the filter paper.
X: It adheres darkly to the filter paper.

(Evaluation method for cumulative hair dyeing)
After applying and drying to 1 g of hair bundle, the evaluation of cumulative hair dyeability after repeated washing twice for hair was evaluated according to the following evaluation criteria.
Evaluation criteria:
A: Equivalent to commercially available oxidative hair dye.
○: No practical problem.
Δ: Slightly difficult to dye
X: Not dyed.

(Evaluation method of coating performance)
The applicability when applied to hair with a hair applicator (filling container) was evaluated according to the following evaluation criteria.
Evaluation criteria:
◯: The amount of liquid adhering to the hair was good and had good applicability.
Δ: The amount of liquid adhering to the hair is slightly reduced, and the applicability is slightly inferior to the above ○.
X: The amount of liquid adhering to the hair decreases, and the applicability is poor.

(Evaluation method for low temperature stability)
100 ml of each hair dye was put in a transparent container with a lid, stored at −10 ° C. for 1 month, and evaluated with the naked eye according to the following evaluation criteria.
Evaluation criteria:
○: There is no precipitate, and the same state as after production is maintained.
Δ: There is some precipitate, but there is no problem in quality and usability.
X: There exists sedimentation (precipitate).

(Evaluation method of dryness after application)
Under 25 ° C.-65 RH%, 0.2 g was applied to 1 g of human hair bundle, touched with a finger every 30 seconds, and the time when adhesion to the finger disappeared was measured and evaluated according to the following evaluation criteria.
Evaluation criteria:
◎: Within 2 minutes ○: Within 4 minutes △: Within 6 minutes ×: Over 6 minutes

(Irritation evaluation method)
Regarding Examples 31 to 21 and Comparative Examples 1 to 12, with respect to 31 samples that can be applied except for Comparative Examples 3 and 9, whether or not to feel irritation is applied at a position as close as possible to the skin of 20 monitors. Confirmation was performed and the evaluation was made according to the following evaluation criteria.
Evaluation criteria:
○: There were no monitors who felt stimulation.
Δ: 1 to 6 monitors felt irritation.
×: 7 or more monitors felt irritation.

(Comprehensive evaluation method)
The following evaluation criteria were evaluated from the above evaluations (6 evaluations) of water resistance, cumulative hair dyeability (5 times), coating performance, low temperature stability, drying property and irritation.
Evaluation criteria:
○: All evaluations of 6 evaluations are more than ○.
○ ': The evaluation of ◯ or more in 6 evaluations is 3 or more, and the evaluation of △ or more is 3 or less.
(Triangle | delta): The evaluation more than (circle) in 6 evaluation becomes 2 or less, and evaluation more than (triangle | delta) becomes 4 or less.
X: One or more x evaluations included in 6 evaluations.

As is apparent from the results of Tables 1 to 3, Examples 1 to 21 which are the scope of the present invention are more resistant to water and accumulated hair (5) than Comparative Examples 1 to 12 which are outside the scope of the present invention. Times), coating performance, low-temperature stability, and drying properties were found to be excellent, and there was no skin irritation.
Looking at the comparative examples individually, Comparative Examples 1 and 2 are resins other than the resin composed of the terpolymer of the present invention, that is, in Comparative Example 1, MERQAT280 (NALCO, resin solid content 40%, polyquaternium- 22, acrylic acid 20%, diallyldimethylammonium chloride 80%). In this case, water resistance is inferior and cumulative hair dyeing is slightly inferior. In Comparative Example 2, CELQUAT SC240C (National Star & Chemical) , Powder, polyquaternium-10, cationized hydroxycellulose). In this case as well, it is understood that the water resistance is slightly inferior, and the cumulative hair dyeing property and the coating performance are inferior.
In addition, when the water content of Comparative Examples 3 and 9 is large, it settles, and when the content of the dye of Comparative Example 4 is large, when the content of the dye of Comparative Example 5 is small, Comparative Examples 6 and When the content of the hair dye assistant of 7 is small or large, when the content of the lower alcohol of Comparative Examples 8 and 9 is large or small, when the content of water and the lower alcohol of Comparative Example 10 is small, When the pH of the hair dyes of Comparative Examples 11 and 12 deviates from 2 to 4, the effects of the present invention [water resistance, cumulative hair dyeability (5 times), coating performance, low temperature stability and drying property] cannot be exhibited. I understand.

It is a partial longitudinal cross-sectional view of the applicator for hair which shows an example of embodiment of this invention. It is a longitudinal cross-sectional view of the side aspect of the applicator for hair which shows the other examples of embodiment of this invention. It is a longitudinal cross-sectional view of the front aspect of the applicator for hair of FIG. It is a longitudinal cross-sectional view of the side aspect of the applicator for hair which shows the other examples of embodiment of this invention. (A) is a perspective view of the applicator for hair of FIG. 4, (b) is a perspective view which shows the state which removed the cap body. It is a disassembled perspective view of the applicator for hair of FIG. It is a longitudinal cross-sectional view of the side aspect of the applicator for hair which shows the other examples of embodiment of this invention. (A) is the perspective view of the assembled applicator for hair of FIG. 7, (b) is the perspective view seen from the bottom part of the applicator for hair.

Explanation of symbols

A hair applicator 10 applicator body 12 core 13 comb part

Claims (9)

0.1 to 3.0% by weight of at least one aqueous acid dye, vinylpyrrolidone represented by the following formula (I), dimethylaminopropylmethacrylamide represented by the following formula (II), and the following formula (III) And a resin composed of a terpolymer composed of alkyldimethylaminopropyl methacrylic acid represented by the formula (1), and the resin content is 0.1 to 2.5% by weight in terms of solid content. A hair dye comprising 1.0 to 20% by weight of an agent, 20 to 60% by weight of a lower alcohol, and 20 to 60% by weight of water and having a pH of 2 to 4.

  The resin is 60 to 90% by weight of vinylpyrrolidone represented by the formula (I), 5 to 30% by weight of dimethylaminopropyl methacrylamide represented by the formula (II), and alkyldimethylaminopropyl methacrylic acid represented by the formula (III). The hair dye according to claim 1, wherein the hair dye comprises 1 to 30% by weight.   The hair dye according to claim 1 or 2, wherein the resin has a weight average molecular weight of 400,000 to 800,000. The content ratio y (wt%) of the water-soluble acid dye satisfies the following formula (IV) when the resin solid content x (wt%) is satisfied. The described hair dye.
0.1 (x + 1) <y ≦ 0.264x + 0.4 (IV)   The content ratio (A) / [(A) + (B)] of water (A) and lower alcohol (B) is 0.3 to 0.7 in weight ratio. The described hair dye.   6. The dye according to claim 1, wherein the hair dyeing assistant is at least one selected from monohydric alcohols, polyhydric alcohols, ether alcohols, lower alkylene carbonates, N-alkylpyrrolidones, and lactones. Hair.   The hair dye according to any one of claims 1 to 6, wherein the hair dye has a viscosity of 2 to 50 mPa · s.   A hair applicator comprising a storage unit for storing the hair dye according to any one of claims 1 to 7.   The tip of the applicator main body is provided with an applicator main body having an application body for applying a hair dye to hair and a comb portion arranged around the application body. Applicator for hair.

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